109433-86-5Relevant articles and documents
Cerium(III) dialkyl dithiocarbamates from [Ce{N(SiMe3)2}3] and tetraalkylthiuram disulfides, and [Ce(κ2-S2 CNEt2)4] from the CeIII precursor; TbIII and NdIII analogues
Hitchcock, Peter B.,Hulkes, Alexander G.,Lappert, Michael F.,Li, Zhengning
, p. 129 - 136 (2004)
The synthesis and characterisation of the first neutral cerium dialkyl dithiocarbamate complexes, using a novel oxidative displacement of the amido ligands of [Ce{N (SiMe3)2}3] by tetraalkylthiuram disulfides [R2NC(S)S]2 (R = Me, Et) in thf solution, are reported. In the absence of other donors, the complexes [Ce(κ2-S2CNMe2)3 (thf)2] 2 and Ce(κ2-S2CNEt2)3 3 were obtained. The addition of a polypyridyl ligand allowed easy access to a range of complexes of general formula [Ce(κ2-S2 CNR2)3(L∩L)][R = Me and L∩L = 2,2′-bipy (4), or 4,7-diphenyl-1,10-phenanthroline (6); or R = Et and L∩L = 2,2′-bipy (5)]. Brief exposure of the Ce(III) dithiocarbamate 3 to oxygen gas afforded in high yield the diamagnetic, crystalline Ce(IV) dithiocarbamate [Ce(κ2-S2CNEt2)4] 7. The neodymium (8) and terbium (10) complexes, isoleptic with 2, were prepared from the appropriate 4f metal (Ln) bis(trimethylsilyl)amide [Ln{N(SiMe3)2}3] [Ln = Nd or Tb (9)] and [Me2NC(S)S]2. The structures of the crystalline complexes 2, 4, 6, 7, 9 and 10 have been determined by X-ray crystallography. Some evidence has been obtained for the formation of the cerium(IV) complex Ce{N(SiMe3)2}2 (κ2-S2CNMe2)2. The cerium(IV) complex 7 has the metal coordinated to eight sulfur atoms of four planar chelating S2CNC2 moieties and its geometry is intermediate between dodecahedral and square prismatic; the mean Ce-S bond length of 2.803 A in 7 compares with the 2.950 A in the Ce(III) complex 2.
Homo- and heterometallic terbium alkoxides - Synthesis, characterization and conversion to luminescent oxide nanostructures
Hemmer, Eva,Huch, Volker,Adlung, Matthias,Wickleder, Claudia,Mathur, Sanjay
, p. 2148 - 2157 (2011)
Terbium alkoxides in homometallic - [Tb3(μ3-OtBu) 2(μ2-OtBu)3(OtBu)4 (HOtBu) 2] (1), [Tb{OC(tBu)3}3(THF)] (2) - and heterometallic configurations - [TbAl(μ
Structurally characterized luminescent lanthanide zinc carboxylate precursors for Ln-Zn-O nanomaterials
Boyle, Timothy J.,Raymond, Rebecca,Boye, Daniel M.,Ottley, Leigh Anna M.,Lu, Ping
, p. 8050 - 8063 (2010/10/03)
A novel family of lanthanide zinc carboxylate compounds was synthesized, characterized (structural determination and luminescent behavior), and investigated for utility as single-source precursors to Ln-Zn-O nanoparticles. Carboxylic acids [H-ORc = H-OPc (H-O2CCH(CH3)2, H-OBc (H-O2CC(CH3)3, H-ONc (H-O 2CCH2C(CH3)3)] were individually reacted with diethyl zinc (ZnEt2) to yield a set of previously unidentified zinc carboxylates: (i) [Zn(μ-ORc)3Zn(μ-ORc)] n [ORc = OPc (1), ONc (2)], (ii) [(py)Zn]2(μ-ORc) 4 [ORc = OBc (3), ONc (4), and py = pyridine], or (iii) Zn(ORc) 2(solv)2 [ORc/solv = OPc/py (5), OcNc/H 2O (6) (OcRc = chelating)]. Introduction of lanthanide cation [Ln[N(SiMe3)2]3, ZnEt2, and HOBc in py] yielded the mixed cationic species structurally characterized as: (i) (OcBc)Ln[(μ-OBc)3Zn(py)]2 [Ln = Pr (7), Nd (8), Sm (9)] or (ii) (py)2Zn(μ-OBc)3Ln(O cBc)2(py) [Ln = Tb (10), Dy (11), Er (12), Y (13), Yb (14)]. Exploration of alternative starting materials [Ln(NO3) 3·nH2O, Zn(O2CCH3) 2, HOBc in py] led to the isolation of (NO3 c)Ln[(μ-OBc)3Zn(py)]2 [Ln = La (15), Ce (16), Pr (17), Nd (18), Sm (19), Eu (20), Gd (21), Tb (22) Dy (23), and Er (24); NO3c = chelating]. The UV-vis spectra of 7-24 revealed standard absorption spectra for the Ln cations. Representative compounds were used to generate nanoparticles from an established 1,4-butanediol-based solution precipitation route. The nanoproducts isolated adopted either a mixed zincite/lanthanum oxide (18n or 22n) or pure zincite (8n or 10n) phase dependent on NO3 or OBc moiety. Fluorescence was not observed for any of these nanomaterials possibly due to phase separation, low crystallinity, surface traps, and/or quenching based on elevated Ln cation content.
